Synthetic resins, photographic process, photographic media, and method of preparing same



Patented June, 1; 1926.

1,587,272 UNITED STATES PATENT OFFICE;

MURRAY C. BEEBE,'ALEXANDER MURRAY, AND HAROLD V. HERLINGER, OI CINCIN- NATLOHIO, ASSIGNORS TO THE WADSWORTH WATCH CASE COMPANY, OF DAYTON, KENTUCKY, A CORPORATION OF KENTUCKY.

SYNTHETIC RESINS, PHOTOGRAPHIC PROCESS, PHOTOGRAPHIC MEDIA, ANEKETHOD OF PREPARING SAME.

170 Drawing.

The present invention relates tothe employment of synthetic resins in photographlc processes, to photographic media, and to methods of=. ,preparing the same.

The primary object is to render available for photographic purposes a class of materials which has not hitherto been known to be available for such purposes.

In accordance with the resent invention or discovery, a suitable p otographic medium comprising a synthetic resin, or synthetic resins, is prepared; and use is made of such medium for various photographic purposes.

- Various kinds of synthetic resins are known, or may be produced. All these resins, apparently, are light-sensitive in some degree, but some of them are very much more light-sensitive than others. In general, it is desirable to associate with synthetic resins a suitable sensitizing agent which will serve to expedite the transformation of the resin under the selective action of light. However, in some instances, it is quite feasible to omit the use of a special sensitizing agent, and still secure the transformation within a reasonably short period of time.

' The present invention pertains broadly to the -use of synthetic resins for photographic purposes. In our application No. 601,827 filed November 18, 1922, is described and claimed that species of the present invention which relates to the use of fivemembered mono-heterocyclic compounds for photographic purposes; in our application No. 603,115, filed November 24, 1922, is described and claimed another modification of the present invention, which pertains to the use in photographic processes of phenolic condensation products; and in our application No. 613,796, filed January 19, 1923, is set forth and claimed anoth r species of the present invention, which pertains more particularly to the use of synthetic resins produced from the five-membered mono-heterof cyclic compounds and amine bodies, with a stated preference for a synthetic resin produced by condensing furfural with B-naphthylamine.

A synthetic resin, associated with a. sensitizing agent. or with such sensitizing agent omitted, depending upon the degree of nat- Application filed. January 19, 1923. Serial No. 618,788.

ural sensitiveness of the resin, or depending upon the particular results desired, may, in I accordance with the resent invention, be subjected to the selectlve action of light in accordance with an image, design or character, and thus there may be produced in the sensitive body, or film, a transformation, resulting in an image, design or character in such body, or film; and the film, or image, may then be developed in any suitable manner.

In general, it is preferred to employ a solution of a synthetic resin, capable of producing a film, or coating, ona suitable support or surface; and with many of the dif-. ferent kinds of resins, it is advlsable to employ special sensitizers, and referably a sensitizer which comprises a halbgen source, or a halogen-liberating compound.

In carrying out the invention, use may be made of various known synthetic resins, amongwhich may be mentioned resins, or resinous substances, derived from the fivemembered mono-heterocyclic compounds referred to in our application No. 601,827, mentioned above; the phenolic condensation products referred to in our application No. 603,115, mentioned above; and other synthetic resins, or resinous compounds, menuse may be madeof synthetic resins pro I duced in accordance with well known methods. It may be added that extended re searches have been made by us with various classes of organic compounds, which, when 'mixed together at room temperature, or

slightly above, have condensedto form viscous polymerization products. Such condensations may be accelerated by the presence of various ingredients, such as iodine, or other halogen. We have found that compounds of a halogen, such as iodoform, or the metal alkyl halides, liberate halogen under the action of light. Such sensitizers may be used advantageously in connection with most of the synthetic resins to contlnue by hoto polymerization, halogenation, or catalytic action, the selective condensation.

The following examples may be given by way of illustration:

(1) Mix together 35 grams of dimethyl aniline,14 grams of benzaldehyde, and 4 grams of iodine; and allow the mixture to stand at room temperature for about three days. There results a viscous green product. Through the addition of 1 gram of iodoform to 10 grams of the resin, there is produced a sensitive coating, which gives a print 1n about two minutes by optical projection in the usual manner.

(2) Mix 15 grams of phenol, 15 grams 40% formaldehyde solution and 1 gram iodine; allow the same to stand at room temperature about forty-eight hours. This results in a resinous condensation product. 10 grams of this resin dissolved in 50 cc. of butyl acetate with 3 grams of iodoform added, produces a sensitive coating, which gives a print in about three minutes. This 1s developable, for example, in 75% alcohol.

(3) Mix together 4 grams of iodine, 10

rams benzaldehyde, 18 grains aniline; alow this mixture to stand overnight. This results in a viscous product, soluble in acetone. Mix 10 grams of this resin with 50 grams of acetone and 3 grams of iodoform. This produces a solution affording a coating which enables a print to be produced with an exposure of forty-five seconds.

(4) Mix 18 grams of aniline, 10 grams 40% formaldehyde and 2 grams iodine. Quite a rapid reaction results at room temperature, resulting in the formation of a yellowish green viscous substance. Mix 10 grams of this initial condensation product with 50 grams of acetone and 3 grams iodoform. This provides a solution which may be applied as a coating to a suitable surface, and the continuing condensation, or trans formation, may be completed satisfactorily by an exposure of forty-five seconds.

(5) Mix 18 grams of benzyl aniline, 4 cc. of 40% formaldehyde solution, 2 cc. of water, and a drop of concentrated hydrochloric acid; heat in a reflux condenser for an hour, thus producing a synthetic resin. 4 grams of this resin dissolved in 30 grams benzol (benzene) and 1 gram iodoform gives a solution, which, in the form of a film, yields a print in thirty seconds. This print may be developed with benzine and turpentine.

(6) Mix 100 grams benzyl chloride, 1 gram of powdered ferric chloride and 3 cc. of concentrated sulphuric acid; heat the mixture for about an hour under a reflux condenser, or until it forms a solid resinous mass. Dissolve 4 grams of this resin in 30 cc. of benzol, to which 1 gram of iodoform is added. This solution will give a dry coating on wh1ch prints may be made by contact, completing the continuing condensation or necessary transformation. in about thirty seconds. Such prints are developable in a mixture of 50 parts of benzine and 50 parts of turpentine.

Reference has already been made to phenolic condensation products. As is well known, such condensation products can be formed by condensing the phenols with active methylene bodies, such as formaldehyde, hexamethylenetetramine, or 'other active methylene body. Resins thus produced can be readily sensitized by means of a small percentage of iodoform, as in the example of the phenolic condensation product given above. Other sensitizing agents may be employed.

Reference also has been made to our pending application No. 601,827, describing the use of condensation products derived from the five-membered mono-heterocyclic compounds, preferably furfural. As was pointed out in said application, some of these furfural resins particularly are very sensitive to light, and may be usefully employed without associating therewith any special sensitizer. In some of the resins of the type just referred to, however, it is advisable to employ special sensitizers, such as sensitizers comprising a halogen source, or a halogenliberating compound.

It will be understood from the description thus far given that it is desirable, or necessary, to use only small percentages of a sensitizing agent, or sensitizing agents, where the use of aspecial sensitizer is required. In all cases, the preliminary condensation is carried far enough to give a suitable resinous body which can, where desired, be placed in solution; and the subsequent condensation is carried on, or effected under the selective action of light, either by contact printing, or by projection, in accordance with an image, design or character. This results in the formation of an image, design or character in the resinous body which differs in solubility, or in a degree of solubility, from those portions of the resin which are not acted upon by the light; and the image may then be developed, or fixed, in accordance with known methods, or any suitable method. Where a halogen-liberating compound is employed as a sensitizing agent, the halogen is liberated under the action of light, and doubtless, serves as a. catalyzing agent, expediting the further reaction which occurs under the action of light. Thus, there is produced under the action of light a continuation of the condensation, forming areas of variable and se-, lective solubility, in accordance with the variable luminous characteristics of the image through which the light is transmitted, or projected.

From the examples given, it will be understood that iodine has the property of greatly promoting con'dcnsations in synthetic resins. Iodoform is very desirable as an accelerating, or sensitizing, agent; and, as indicated above, the metal halides may be used advantageously. The sensitizing agent employed may comprise one or more of any suitable sensitizers. While iodine has been specifically mentioned as a halogen for use in the process, other halogens, such as chlorine, or bromine, may be used, or halogen-liberating compounds comprising these materials may beused.

A useful method of employing the invention is that of covering a suitable surface with a light-sensitive coating; and exposing the same to a luminous image, by optical projection, or by contact printing. In gen eral, the meth s known in the art may be followed. After the prints have been formed, they may be developed in any-suitable manner. Any solvent that willreact on the parts of the coating which have not been acted upon by light, or vice versa, may

. be used, as desired. In short, any suitable method of developing, or fixing, the print, or image, may be employed.

, As has been indicated, the preliminary condensation may be brought about in any suitable manner, as by heat, the use of condensing reagents, or by preliminary exposure to light in the presence of a catalyst; andthe subsequent transformation may be effected either in the presence of a special sensitizer, or without such special sensitizer, depending upon the efl'ects desired.

Suitable resinous compounds are produced by combining a wide variety of substances, those referred to above being given as examples. It is immaterial whether the preliminary condensation is initiated or effected by a halogen, or in any other manner.

It may be stated that most of the condensation reactions are accelerated by the addition of a halogen, particularly under the .action of light.

Even though we have predicated our invention on the preliminary condensation effect and a further continuing condensation produced by'the selective action of light, we

do not exclude those materials which operate practically in the same manner, even though the initial product formed may not be technically regarded as a preliminary condensation product. For example, some of thefurfural resins, in their initial stages, may

be regarded by some as not being true synthetic resins. but rather as being in the nature of addition products. In any case, however, for the purpose of the present invention, these initial products act like pre- 'light astransmitted, or-projected, through an image, design or character.

Whlle it is preferred to employ these light-sensitive bodies in the form of varnishes or lacquers, it is to be borne in' mind that the bodies themselves possess the capability of transformation under the action of light. Hence, we do not limit ourselves to the use 'of such bodies in solution.

Various uses to which the invention may be put will occur to those skilled in the art ofphotographic processes as employed in the industrial arts. and specific enumeration of the same herein is unnecessary.

The foregoing detailed description has been given for clearn ess of understanding only, and no unnecessary limitations should be understood therefrom, but the appended claims should be construed as broadly as permissible.

What we regard as new, and desire to secure by Letters Patent, is: 1. A photographic process comprising: preliminarily forming a synthetic resinous compound which is capable of condensation under the action of light: and subjecting the same to the selective action of light in accordance with a luminous image to etfectthe desired transformation.

2. A photographic process comprising: preliminarily forming a synthetic resinous compound which is capable of condensation under the action of light; subjecting the same to the selective action of light in accordance with a luminous image to effect the desired transformation; and developing the image.

3. A photographic process comprising: forming a coating comprising a solution of a synthetic resinous compound susceptible of being condensed under the action of light; and subjecting said coating to the selective action of light in accordance with a luminous image to effect selective condensation.

4. A photographic process comprising: forming a coating comprising a solution of a synthetic resinous compound susceptible of being condensed under the. action of light; and subjecting said coating to the selective action of light in accordance with a lumiof light to the selective action of light in ac cordance with a luminous ima e until the desired transformation is efi'ecte and developing the print. i

7. A photographic process wh1ch comprises: subjecting to the selectiye action of light in accordance with a luminous image a body comprising a synthetic resin and an associated sentitizing agent.

8. A photographic process which comprises: subjecting to the selective action of light in accordance with a luminous image a body con'u'nising a synthetic resin and an associated sensitizing agent comprising a halogen source.

9. A photographic process which comprises: subjecting to the selective action of light in accordance with a luminous image a body comprising a synthetic resin and an associated sensitizing agent comprising a halogen-liberating compound.

10. A photographic process which comprises: subjecting to the selective action of light in accordance with a luminous image a body comprising a synthetic resin and an associated sensitizing agent comprising a halogen-substituted hydrocarbon.

11. A photographic process which comprises: subjecting to the selective action of light in accordance with a luminous image a body comprising a synthetic resin and an associated sensitizing agent comprising iodoform.

12. A photographic process whichcomprises: subjecting to the selective action of light in accordance with a luminous image a body comprising a synthetic resin and an associated sensitizing agent comprising a halogen-substituted hydrocarbon and a metallic halide.

13. A photographic process which comprises: applying to a surface a coating comprising an artificial resinous compound capable of being condensed under the action of light, such compound having associated therewith a sensitizing agent; and subjecting said coating to the selective action of light in accordance with a luminous image and thereby selectively changing the coating into variable condensation areas.

14. A photographic process which com prises: applying to a surface a coating comprising an artificial resinous compound capable of being condensed under the action of light, such compound having associated therewith a sensitizing agent; subjecting said coating to the selective action of light 1n accordance with a luminous image and thereby selectively changing the coating into variable condensation areas; and developing the coating.

15. A photographic process which comprises: applying to a surface a coating comprising a solution of a synthetic resin and sensitizing agent; and effecting transformation of said coating selectively by acting thereon with light in accordance with a lumi nous image.

16. A photographic process which comprises: applying to a surface a coating comprising a solution of a preliminary condensation product and an associated sensitizing agent; and selectively transforming said coating by the action of light in accordance with a luminous image.

17.-A photographic process which com prises: applying to a surface a coating comprising a solution of a preliminary condensation product and an associated sensitizing agent; selectively transforming said coating by the action of light in accordance with a luminous image; and developing the coating.

18. A' photographic process which comprises: applying to a surface a coating comprising a solution of a resinous compound capable of being condensed under the action of ight, such compound having associated therewith a sensitizing agent comprising a halogen source; and acting on said coating selectively with light in accordance with a luminous image.

19. A photographic process which cornprises: applying to'a surface a coating comprising a solution of a resinous compound capable of being condensed under the action of light, such compound having associated therewith a sensitizing agent comprising a halogen-liberating compound; andv acting on said coating selectively with light in accordance with a luminous image.

20. A process which comprises: subjecting to the selective 'action of light in accordance with a luminous image a body comprising a resinous condensation product of benzaldehyde.

21. A process which comprises: subjecting to the selective action of light in accordance with a luminous image a body comprising a resinous condensation product of henzaldehyde and aniline.

22. A process which comprises: subject ing to the selective action of light in accordance with a luminous image a body comprising a condensation product of benzaldehyde. associated with a halogen-liberating agent.

23. The process of producing a photographic medium which comprises incorporating with a synthetic resin compound capable of being condensed under the action of light a sensitizing agent adapted to accelerate the action of light in a photographic action.

24. The process of producing a photographic medium which comprises incor-' porating with a preliminary condensation product a sensitizing agent.

25. The process of forming a photographic medium which comprises incorporating with a preliminary condensation product which is capable of further con- I poratin'gwith a prelimina densation under the action of light a sensitizing agent comprising a halogen-liberating und.

27. The process of forming a photographic medium which comprises'incorcondensation product which is capable o rther condensation under the'actlon of light a. sensitizing agent comprising a halogen-substituted hydrocarbon.

28. The process of forming a photocompo graphic medium which comprises incorporating with a preliminary condensation product which is capable of further condensation under the action of light a sensitizing agent comprising iodoform. v

'29. A photographic medium comprising a synthetic resin compound capable of being condensed under the action of light, and a sensitizing agent incorporated there with adapted to accelerate the action of light under photographic action.

30. A photographic medium comprising a resin compound capable of being condensed under the action of light, and a. sensitizing agent incorporated therewith comprising a halogen-liberating compound.

31. A photographic medium comprising a resin compound capable of being condensed under the action of light, and a sensitizing agent incorporated therewith comprising a halogen-substituted hydrocarbon. 32. 'A photographic medium comprising a resin compound capable of being condensed under the action of light, and a sensitizingagent incorporated therewith comprising iodoform. I

33; A photographic medium com rising a solution of-a resincompound 'capab e of being condensed under the action of light, as sociated with a sensitizing agent.- 1 p 34. A photographic medium-comprising a' solution of a resincompound capable of being condensed under the action of light, associated with a sensitizing agent comprising a halogen-liberatin compound.

- 35. 'A photograp ic medium comprising asolution of a resin compound capable of be ing condensed under the action of light, as sociated with a sensitizing agent comprising iodoform; a

36. A print comprising a synthticresin embodying a photographically formed im age,design or character.

37. A print comprising a condensation product of benzalde yde embodying a photographically formed image, design or character.

In testimony whereof. we. aflix our signatures.

; I MURRAY 0. BEEBE.

ALEXANDER MURRAY. HAROLD v. HERLINGER. 

